EP1183225B1 - Procede de production d'esters d'acides gras d'alcools alkyliques monovalents - Google Patents

Procede de production d'esters d'acides gras d'alcools alkyliques monovalents Download PDF

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EP1183225B1
EP1183225B1 EP00943778A EP00943778A EP1183225B1 EP 1183225 B1 EP1183225 B1 EP 1183225B1 EP 00943778 A EP00943778 A EP 00943778A EP 00943778 A EP00943778 A EP 00943778A EP 1183225 B1 EP1183225 B1 EP 1183225B1
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oil
transesterification
fatty acid
process according
acid esters
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EP1183225A1 (fr
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Ralf TÜRCK
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AT Agrar-Technik GmbH
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AT Agrar-Technik GmbH
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/02—Refining fats or fatty oils by chemical reaction
    • C11B3/06—Refining fats or fatty oils by chemical reaction with bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • Fatty acid esters of monohydric alkyl alcohols can be found in the chemical and pharmaceutical industries both as raw material as well as various uses as intermediates. About that such connections also come in the Food industry and especially recently also used as diesel fuel.
  • the above-mentioned oils often also contain not inconsiderable amounts of free fatty acids, their Presence also has a negative impact. As free acids these substances react with the to form soap basic catalyst added for the transesterification. As a result, part of the catalyst is neutralized and is therefore no longer available for the transesterification reaction Available. To solve this problem, the free Neutralizes fatty acids before the actual transesterification and / or be removed, or else it must be a corresponding one larger amount of basic catalyst can be added (WO 92/00268).
  • EP-A-0 131 991 discloses a process for the transesterification of Fatty acid esters, which is carried out under base catalysis becomes. Furthermore, the used in this process Fatty acid esters by pretreatment with harmful base Free of accompanying substances. The transesterification reaction is carried out in one Counterflow reactor carried out, and is therefore for small Systems not practical.
  • the present invention is therefore based on the object a simple and economical process for Production of fatty acid esters of monohydric alkyl alcohols to provide the lowest possible requirements for the Starting oils provides, and at the same time high yields guaranteed.
  • the method according to the invention is illustrated in FIG. 1 explained.
  • the advantages achieved are in particular that starting oils with a high content of free fatty acids, which can also contain mucilages, easily to fatty acid esters of monohydric alkyl alcohols can be processed.
  • Process according to the invention only catalytic amounts of base needed so that additional expenses for Catalyst material for neutralizing the free acids in generally not applicable because the transesterification step Amount of catalyst in the extraction step for the Neutralization step is available.
  • the method according to the invention provides simplifications Product with high purity and in very good yield.
  • reaction conditions of this pretreatment are only limited by the solidification point of the raw material. Under from the point of view of economy, this should be considered Ambient temperature and pressure, at higher Solidification points about 10 ° C above this point and Ambient pressure.
  • the choice of the basic glycerin phase is variable. It must just be guaranteed that at least as much free catalyst is present that all free fatty acids can be neutralized. As a rule, the proportion is sufficient of free catalyst from the one coming from the transesterification basic glycerin phase also for raw materials with a high proportion free fatty acids.
  • Has the basic glycerin phase a glycerol content of 20-99%, preferably 40-60%.
  • the Catalyst content is between 1 - 30%, preferably 5 - 10 %.
  • the proportion of transesterification alcohol is between 5 - 40%, preferably 15-25%.
  • the amount of basic glycerin phase added based on the raw material fluctuates between 1 - 100%, preferably 5-15%.
  • the basic glycerol phase can also required by adding solid alkaline catalyst or an alcohol / catalyst mixture can be added.
  • the Glycerin extractant can also be mixed directly from glycerols of various qualities, technically to Pharma, and alkaline catalyst with or without alcohols getting produced.
  • Main group of the periodic table preferably NaOH, KOH and sodium alcoholates such as e.g. Sodium.
  • the Reaction mixture separated by simple sedimentation are then immediately transesterified become.
  • Usual sedimentation times are 15 min - 72 h, preferably 1 - 3h.
  • the temperature of the raw material should lie above the solidification point.
  • vegetable oils such as Rapeseed, soybean and sunflower oil is an ambient temperature of 20 ° C is sufficient, for carcass and fryer fat 40 - 50 ° C are realistic.
  • the Sedimentation temperature between 0 - 100 ° C, preferred 20 - 40 ° C.
  • Triglyceride directly with base to carry out the transesterification the fatty acid ester of polyhydric alcohols to fatty acid esters monohydric alkyl alcohols are added. To this end it is transferred to a stirred tank.
  • the amount of alkyl alcohol used for the transesterification is divided into 1 to 10, preferably 2 Transesterification stages. Overall, for the invention Process about 1.05 - 2 moles of alcohol per mole of bound Fatty acid proportions used, preferably 1.2-1.4 mol. In the The usual two-stage procedure is carried out in the first stage 40-99%, preferably 90-95%, and in the second stage 1-60%, preferably 5-10% used.
  • alkyl alcohol to be used is here Procedure not further restricted. However, are preferred linear, branched or cyclic alkyl alcohols with 1-10 Carbon atoms, particularly preferred is methanol.
  • the base catalyzing the transesterification reaction in which it advantageous to metal hydroxides and / or alcoholates especially of metals from I. to III. Main group of the Periodic table, the reaction mixture can both in solid form as well as in the form of an alcoholic solution be added. Potassium hydroxide is special as a base prefers.
  • the 25 - 50 wt .-% base based on the Total weight of the solution included. That way the amount of alcohol entered is of course in the Include the total amount of alcohol.
  • the total amount of base used in this step is added depends on the other Procedure and the nature of the Starting material. In the case of single-stage transesterification, this level, of course, the total amount of basic Transesterification catalyst used, whereas one two-stage transesterification in this stage only 20 - 95%, and preferably 80-90% of the total amount can be used.
  • the minimum amount of basic transesterification catalyst is at low content of free fatty acids (low acid number; Inequality (I) is fulfilled) by the transesterification reaction specified and can be determined according to equation (II). at higher acid numbers (inequality (I) is not fulfilled) the neutralization of the free fatty acids to the determining Step for the calculation of the required Amount of catalyst.
  • the one to be used Minimum amount of base determined using equation (III) become.
  • the numerical value 0.088 mol / 1000 g oil is an empirical one determined minimum value, which was determined so that a acceptable response speed is guaranteed. Of this amount represents 0.084 mol / 1000 g of oil for the Neutralization of free fatty acids available; the Ratio 0.084 / 0.088 can thus be used as a recycling yield be understood.
  • reaction time in this stage is 5-60 min, and preferably 25-35 min. Since this stage is also preferred Ambient temperature and pressure is carried out exact reaction time to the respective conditions adapt.
  • Equation (V) corresponds to Equation (II)
  • the second term takes into account the recycled amount of basic Glycerin phase in the transesterification step.
  • Equation (VI) is that Equivalent to equation (III). The minimum amount required according to this equation is higher than that according to equation (III), since only the 1-X portion of the basic glycerol phase for the neutralization of the free fatty acids is used. The Reuse the basic glycerin phase for the Transesterification finds its limits where it is no longer sufficient Base for the neutralization of the free fatty acids in the portion 1-X is present. Therefore, the optimal combination of amount of base and reuse fraction X used taking into account equals (V) and (IV) be determined.
  • equations (V) and (VI) By equating equations (V) and (VI) and transforming a quadratic equation can be obtained whose only physically sensible solution a value of X im Range from 0 to 1 returns. This, maximum for that Possible fraction X to be used for transesterification can be found below then be used in equations (V) or (VI) to get the to determine the minimum amount of catalyst required.
  • the reaction mixture can be worked up in a suitable manner, the phase separation has proven to be particularly advantageous.
  • the advantage of this dimensioning is can be seen in the fact that this settling tank as a reservoir can be used, on the one hand, the settling times longer than that required for pretreatment and transesterification Can be time and on the other hand continuous Product removal becomes possible.
  • This container should continue to be designed so that the emerging residual phase, which includes the multivalued Contains alcohols, and those monohydric at fatty acid esters Alcohol rich phase by two in different places attached outlets can be removed.
  • reaction mixture it has proven advantageous for the reaction mixture to be approximately in What is the amount of the liquid-liquid phase boundary an appropriately attached or trained inlet can be achieved and the ester-rich phase as far as possible decrease away from the phase boundary, i.e. the outlet for the ester-rich phase should be as close as possible to the Level limit of the container used for phase separation to be appropriate.
  • a second transesterification is always appropriate if one as complete a transfer as possible in the starting product contained fatty acid residues in fatty acid esters monovalent Alkyl alcohols is desired.
  • the separated one Phase in a second reactor which is advantageous as Stirred kettle is designed, transferred and with alkyl alcohol and Base under the same reaction conditions as in the first transesterification stage implemented.
  • alkyl alcohol in an amount of 5-80%, preferably added from 10-20% of the total amount mentioned above as the one used in the previous steps Alkyl alcohol in the phase separation essentially in the Glycerin phase migrates.
  • the required amount of alcohol can either be added directly be mixed with the base and then in be directed to the reactor. Again, the should same alkyl alcohol or the same alkyl alcohol mixture as used in the previous stages.
  • the reaction time in this stage is 15-45 min, and preferably 25-35 min.
  • Alkyl alcohol rich fraction can be driven out.
  • an evaporator is advantageously used in which the last fraction separated over a first 90 to 120 ° C hot surface is conducted and the low boiling ingredients on a second surface be put down.
  • 500 g of cold-pressed rapeseed oil containing free Fatty acids (FFA content) of 0.3% are at 293 K in one Beaker with stirring with 52.5 g of methanol (99.7%) and 25 g a 30% by weight solution of KOH (85%) in methanol added.
  • the agitator is switched off after about 25 minutes.
  • the mixture is transferred to a separatory funnel, so that after about 3 hours the two liquid phases in two Containers can be collected.
  • the biodiesel is made by Add 2 g of a 30% solution of KOH in methanol completely transesterified, and finally washed and dried.
  • the yield is 495 g (99%) of rapeseed methyl ester and 82.5 g basic glycerol phase with the following composition: approx. 65% glycerin, approx. 18% methanol, approx. 17% free KOH and Potassium soaps.
  • step a The 495 g of cold-pressed rapeseed oil from Example 1 (step a) are mixed with 29.3 K in a beaker with stirring with 59.3 g of methanol (99.7%) and 12 g of a 33% strength by weight solution of KOH (85% strength) in methanol. After about 25 minutes the agitator is switched off and the mixture is transferred to a separating funnel. After about 1 hour, the two liquid phases are collected in two containers. The biodiesel is completely transesterified by adding 3 g of a 33% solution of KOH in methanol, the resulting glycerol phase is separated off and combined with the first, and the biodiesel is then washed and dried.
  • the yield is 492.5 g (99.5%) of rapeseed methyl ester and 73 g of basic glycerol phase with the following composition: approx. 68% glycerin, approx. 20% methanol, approx. 4% potash soaps, approx. 7% free KOH and approx. 1% water.
  • the total yield based on the raw material before extraction is 98.5%.
  • Example 1 (step b) was used.
  • the amounts used, reaction conditions and yields are summarized in Table 3.
  • Example 4 With an identical free fatty acid content of 5% in Example 4 and Comparative Example 4 is the overall yield according to the method of the present invention with 92.6% significantly higher than with the conventional method (80%).
  • the overall yield is also 86.6% for the transesterification of animal body fat by the method of the present Invention (Example 5) much better than after conventional methods (60%; comparative example 5), and that even with a higher proportion of free fatty acids (Example 5: 12% FFA; Comparative Example 5: 9% FFA).

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
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Claims (20)

  1. Procédé de production d'esters d'acides gras d'alcools alkyliques monovalents par transestérification sous catalysation basique de triglycérides issus d'huiles et/ou de graisses naturelles ou synthétiques, contenant des acides gras libres, à titre de substances d'accompagnement perturbatrices,
    où, d'abord, on traite les huiles et/ou les graisses avec une phase glycérine basique non miscible, de manière que les acides gras libres soient neutralisés et se transforment en phase glycérine et, ensuite,
    les triglycérides, après séparation de la phase glycérine, étant transestérifiés en les esters d'acides gras, avec des alcools monovalents avec utilisation d'une base comme catalyseur, dans un récipient d'agitation,
    caractérisé en ce que l'on utilise lors de la transestérification des triglycérides la phase glycérine basique apparaissant, après séparation des esters d'acides gras, pour le traitement des huiles et/ou des graisses, dans le but d'éliminer les acides gras libres, la quantité minimale de catalyseur utilisée, rapportée à 1000 g de l'huile à traiter, étant calculée, en fonction de l'indice d'acidité et de la masse molaire moyenne de l'huile, selon les équations (I) à (III) :
    pour un indice d'acidité SZ, qui satisfait l'inéquation (I): SZ < (0,084 mole/1000 g d'huile) * M(KOH) * Y
    selon l'équation (II) Quantité minimale de catalyseur/1000 g d'huile = 0,088 mole/1000 g d'huile * Y
    Et, autrement, selon l'équation (III) Quantité minimale de catalyseur/1000 g d'huile = (SZ / M (KOH)) * (0.088 / 0.084), avec
    Y = (880 g/mol) / (masse molaire moyenne de l'huile utilisée) et
    SZ = indice d'acidité de l'huile utilisée [(g KOH)/(1000 g d'huile)]
  2. Procédé selon la revendication 1, dans lequel on ajoute aux triglycérides obtenus après prétraitement avec une phase glycérine basique non miscibles, dans le but d'effectuer la transestérification, une base et un alcool alkylique et, après la transestérification, on sépare une fraction, riche en esters d'acides gras, d'alcools alkyliques monovalents, la première fraction séparée, riche en esters d'acides gras d'alcools alkyliques monovalents, étant mélangée à une base et à de l'alcool alkylique dans le but d'obtenir une transestérification supplémentaire et, après la transestérification, une deuxième fraction, riche en esters d'acides gras d'alcools monovalents, étant séparée.
  3. Procédé selon la revendication 1 ou 2, dans lequel on utilise comme base des hydroxydes et/ou des alcoolats métalliques ou bien leurs solutions dans un alcool alkylique.
  4. Procédé selon l'une des revendications précédentes, la séparation des fractions, riches en esters d'acides gras, d'alcools alkyliques monovalents se faisant par séparation des phases.
  5. Procédé selon l'une des revendications précédentes, où, avant la dernière séparation des phases chaque fois effectuée, le mélange de réaction est lavé avec 5 % en poids d'eau ou plus, en se référant au poids du mélange, contenant un ester d'acide gras, utilisé dans cette étape.
  6. Procédé selon la revendication 5, où après la dernière séparation de phase chaque fois effectuée, on chasse les composants à faible point d'ébullition de la fraction riche en esters d'acides gras d'alcools alkyliques monovalents.
  7. Procédé selon l'une des revendications 4 à 6, où, pour effectuer la séparation des fractions riches en esters d'acides gras d'alcools alkyliques monovalents, on utilise un récipient dans lequel le mélange initial respectif est amené à ou au-dessous de la limite de phase liquide-liquide et la fraction à séparer est prélevée dans le tiers supérieur du récipient.
  8. Procédé selon la revendication 6 ou 7, où, pour chasser les composants à faible point d'ébullition, on utilise un évaporateur pour lequel la dernière fraction séparée est guidée sur une première surface chaude, d'une température de 90 à 120°C. et les composants à faibles point d'ébullition étant déposés sur une deuxième surface.
  9. Procédé selon au moins l'une des revendications précédentes, des huiles végétales étant utilisées comme matériau de départ.
  10. Procédé selon au moins l'une des revendications précédentes, des alcools alkyliques, comportant de 1 à 10 atomes de carbone, étant utilisés.
  11. Procédé selon au moins l'une des revendications précédentes, où le prétraitement est effectué avec la phase glycérine basique, dans un récipient d'agitation, sur une durée de 1 à 60 min.
  12. Procédé selon la revendication 11, la durée du prétraitement étant de 5 à 15 min.
  13. Procédé selon au moins l'une des revendications précédentes, où de 5 à 15 % de la phase glycérine basique produite lors de la transestérification sont utilisés dans l'étape de prétraitement.
  14. Procédé selon au moins l'une des revendications 1 à 12, où, en plus de la phase glycérine basique produite lors de la transestérification, d'autres glycérines et/ou bases sont utilisées pour l'élimination des acides gras libres.
  15. Procédé selon la revendication 14, où, en plus, est utilisée de la glycérine technique ou de la pharmaglycérine, dans laquelle sont dissous KOH, NaOH, ou de l'éthylate de sodium.
  16. Procédé selon au moins l'une des revendications précédentes, la quantité globale utilisée de catalyseur basique de transestérification étant de 1 à 4 fois la quantité minimale de catalyseur selon la revendication 1.
  17. Procédé selon l'une ou plusieurs des revendications précédentes, la quantité globale d'alcool utilisé étant de 1,2 à 1,4 mole par mole de fraction d'acide gras liée.
  18. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce qu'une proportion X de la phase glycérine basique, apparaissant lors de la transestérification des triglycérides, est réutilisée pour la réaction de transestérification, après séparation des esters d'acides gras, l'indice d'acidité satisfaisant à l'inégalité (IV) : SZ < (0,084 mole/1000 g d'huile) * M(KOH) * Y et la quantité minimale à utiliser de catalyseur (en se référant à 1000 g de l'huile à traiter), ainsi que la fraction X de la phase glycérine basique à réutiliser pour la transestérification, étant choisies de manière que l'on satisfasse simultanément aux équations (V) et (VI) : Quantité minimale de catalyseur/1000 g d'huile = (0,088 mole/1000 g d'huile - (X * 0,084 mole/1000 g d'huile)) * Y Quantité minimale de catalyseur/1000 g d'huile = (SZ / M(KOH) * (0,088 / (0,084 * (1 - X)) avec
    Y=(880 g/mole) / (masse molaire moyenne de l'huile utilisée)
    SZ = indice d'acidité de l'huile utilisée [(g KOH)/(1000 g d'huile)]
    X = proportion de la phase glycérine basique réutilisée pour la transestérification.
  19. Procédé selon au moins l'une des revendications précédentes caractérisé en ce que les acides gras libres séparés avec la phase glycérine basique, où leurs sels sont soumis à une post-estérification avec un alcool alkylique.
  20. Procédé pour la fabrication de carburant pour des moteurs diesel comprenant un procédé de fabrication d'esters d'acides gras d'alcools alkyliques monovalents selon l'une des revendications 1 à 19.
EP00943778A 1999-06-07 2000-06-07 Procede de production d'esters d'acides gras d'alcools alkyliques monovalents Expired - Lifetime EP1183225B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200030252T SI1183225T1 (en) 1999-06-07 2000-06-07 Method for producing fatty acid esters of monovalent alkyl alcohols

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19925871 1999-06-07
DE19925871A DE19925871A1 (de) 1999-06-07 1999-06-07 Verfahren zur Herstellung von Fettsäureestern einwertiger Alkylalkohole und deren Verwendung
PCT/EP2000/005255 WO2000075098A1 (fr) 1999-06-07 2000-06-07 Procede de production d'esters d'acides gras d'alcools alkyliques monovalents, et utilisation de ces esters

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EP1183225A1 EP1183225A1 (fr) 2002-03-06
EP1183225B1 true EP1183225B1 (fr) 2003-09-03

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US (1) US6538146B2 (fr)
EP (1) EP1183225B1 (fr)
AT (1) ATE248798T1 (fr)
AU (1) AU5812500A (fr)
CZ (1) CZ297802B6 (fr)
DE (2) DE19925871A1 (fr)
EA (1) EA004051B1 (fr)
ES (1) ES2206267T3 (fr)
HU (1) HUP0201656A3 (fr)
PL (1) PL205257B1 (fr)
PT (1) PT1183225E (fr)
WO (1) WO2000075098A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4071226A1 (fr) 2021-04-08 2022-10-12 AT Agrar-Technik Int. GmbH Processus pour produire des esters d'alkyle d'acides gras

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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WO2002046339A2 (fr) 2000-12-04 2002-06-13 Dr. Frische Gmbh Procede de pretraitement d'huiles brutes et de graisses brutes pour la production d'esters d'acides gras
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EA004051B1 (ru) 2003-12-25
ATE248798T1 (de) 2003-09-15
EP1183225A1 (fr) 2002-03-06
WO2000075098A1 (fr) 2000-12-14
US20020156305A1 (en) 2002-10-24
PL352527A1 (en) 2003-08-25
DE50003549D1 (de) 2003-10-09
AU5812500A (en) 2000-12-28
PL205257B1 (pl) 2010-03-31
ES2206267T3 (es) 2004-05-16
HUP0201656A3 (en) 2003-08-28
EA200101267A1 (ru) 2002-06-27
DE19925871A1 (de) 2000-12-21
US6538146B2 (en) 2003-03-25
CZ20014388A3 (cs) 2002-05-15
CZ297802B6 (cs) 2007-04-04
HUP0201656A2 (en) 2002-09-28

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